Metallized disazo dyes containing a monochlorotriazine substituent



.* 3,057,846 Patented Oct. 9, 1962 the phenylene or naphthylene radical B there may be 3,057,846 mentioned sulpho, carboxy, chloro, alkoxy for example METALLEZED DIAZO DYES CONTAHNENG A methoxy and ethoxy, alkyl for example methyl and ethyl MONOCHLOROTRIAZINE SUBSTITUENT and acylamino for example acetylarnino and benzoyl- Herbert Francis Andrew and Alec Mee, Manchester, Eng- 5 amino land, assignols t Imperial Chemical Industries Limited According to a further feature of the invention there gg ggg ghg gfi fij ggg gzi fi g is provided a process for the manufacture of the new azo Ciaims Priority appficafim Great Britain Apr. 22, 1959 dyestuffs, as hereinbefore defined, which comprises dia- Claims (Cl. 260 146) zotising an amine of the formula:

This invention relates to new azo dyestufis and more B NH2 particularly it relates to new water-soluble azo dyestufis I which are valuable for colouring cellulose textile ma- 5' terials.

According to the invention there are provided the new F 1 I azo dyestufis which, in the form of the free acids, are 0mm a represented by the formula: wherein A and B have the meanings stated above, and

On-lHZn-l OH N--LG O- I /N L r a A-N=N B N=N J N t wherein A represents a phenyl or naphthyl radical which coupling the diazo compound so obtained with a coupling may optionally be substituted by halogen atoms or by component of the formula:

alkyl or alkoxy radicals containing not more than 4 car- OMHBH bon atoms or by hydroxy, sulphonic or carboxylic acid r groups,,R represents a hydrogen atom or an alkyl radi- OH N L cal containing not more than 6 carbon atoms, X represents N a chlorine or a bromine atom, Y represents an amino N group or an aryl, aryloxy or an alkylamino radical or an arylamino, sulphoarylamino or carboxarylamino radical I wherein the aryl residue contains not more than 12 carbon Y atoms, In represents 1 or 2, n represents 1, 2, 3, 4 or 5, (503mm p represents 1 or 2 and the phenylene or naphthylene Formula II radical B can carry further substituents.

As examples of the alkyl or alkoxy radicals containing not more than 4 carbon atoms which may be present in the phenyl or naphthyl radical represented by A there may be mentioned methyl, ethyl, propyl, butyl, methoxy and Y- solution of hydrochloric acid, adding the dia'zo solution AS examPles of the alkyl Tadlcal cont'fumng not more or suspension so obtained to an aqueous solution of the than 6 carbon atoms represented by R there may be coupling component of Formula II, adding sodium carmentloned methyl: ethyl, P P butylbonate to maintain the pH of the mixture between 6.5 As examples of the aryl radicals represented by Y and 7 and filtering off the azo dyeshlflg which is there may be mentioned phenyl and tolyl, as an example cipitated. If desired sodium chloride can be added to of the aryloxy radicals represented by Y there may f ensure complete precipitation of all the azo dyestuif. mentloned phenoxy: as examples the alkylammo The amines of Formula I may themselves be obtained cals represented by Y there may be mentioned methylby diazotising a primary amine of the formula: amino, dlmethylamino and d1(5hydrXyethY1)am1n as wherein A has the meaning stated above, and coupling wherein R, X, Y, m, n and p have the meanings stated above.

This process of the invention may be conveniently carried out by adding sodium nitrite to a solution or suspension of the amine of Formula I in a dilute aqueous examples of the arylamino radicals represented by Y there the diam compound so obtained with a para coupling may be mentioned naphthylamino, phenylamino and hymine of the formula:

droxyphenylamino, as examples of the carboxyarylamino radicals represented by Y there may be mentioned 2-, 3- B NHI or 4-carboxyphenylamino and as examples of the sulphoarylamino radicals represented by Y there may be mentioned 2-, 3- or 4-sulphophenylamino, sulphonaphthylamino and 3:5-disulphophenylamino. wherein B has the meaning stated above. If desired the As examples of substituents which may be present in para coupling amine may be used in the form of the a I w-methane sulphonate; this group being subsequently re- As examples of the naphthol sulfonic acids of Formula moved after coupling by treatment with alkali. HI which may be used to obtain the coupling components As examples of the primary amines of the formula: of Formula II used in this process of the invention there ANH2 Which may be used to obtain the amines of may be mentioned 1-amino-8-naphthol-3:6-disulphonic Formula I used in this process of the invention there may acid, 1-(3'- or 4'-aminobenzoylamino)-8-naphthol 3:6-dibe mentioned aniline, orthanilic acid, metanilic acid, sulsulphonic acids, 1-N-ethylamino-8-naphthol 3:6 disulphanilic acid, S-amino-Z-hydroxybenzoic acid, S-amino-Z- phonic acid, l-N-butylamino-8-naphthol-3:6-disulphonic hydroxy-B-sulphobenzoic acid, Z-naphthylamine 6- or 8- acid, 1-amino-8-naphthol-4:6-disulphonic acid, l-N butylsulphonic acid, l-naphthylamine 4-, -5-, -6-, or -7-sularnino-8-naphthol-4:6-disulphonic acid, 1-(3- or 4-aminophonic acid, l-amino-S-naphthol 3:6-disulphonic acid, 10 benzylamino)-8-naphthol-4:6-disulphonic acid, l-amino- 2:S-dichloroaniline-4-sulphonic acid, 5-chlor0-4-methyl- 8-naphthol-4-sulphonic acid and 1-amino-8naphthol-3- aniline-Z-sulphonic acid, 4-methoxyaniline-2-sulphonic sulphonic acid.

acid, 3-chloro-4-methylaniline-2-sulphonic acid, 4-chloro- As examples of the triazines of Formula IV which may aniline-Z-sulphonic acid, 4-chloro-3-methylaniline-6-sulbe used to obtain the coupling components of Formula phonic acid, 4-chloroaniline-3-sulphonic acid, aniline-2:4- II used in this process of the invention there may be disulphonic acid, aniline-2:5-disulphonic acid, anthranilic mentioned 2-phenyl-4z6-dichloro-lz3z5-triazine, Z-aminoacid, 5-sulphoanthranilic acid, 4-sulphoanthranilic acid, 4:6-dichloro-l:325-triazine, 2-methylamino-4:6-dichloro- Z-methoxy-l-naphthylamine-6-sulphonic acid, Z-ethoxy-l- 1:3:5-triazine, 2-diethy1amino-4:6-dichloro 1:325 triaznaphthylamine-6-sulphonic acid, 2-naphthylamine 1:5-, ine, 2-phenylamino-4:6-dichloro-1:3:5 -triazine, 2-(2- 3:6-, 4:8-, 5:7- or 6:8-disulphonic acid, 2-naphthylaminesulphophenylamino) 4:6 dichloro-1:3:5-triazine, 2-(3- l-sulphonic acid, Z-naphthylamine 3:6:8-trisulphonic acid, sulphophenylamino)-4:6-dichloro 123:5 triazine, 2-(4'- and 4sulpho-2-aminoanisole. sulphophenylamino) 4:6 dichloro-l :3 :S-triazine, 2-(2- As examples of the para coupling amines which may carboxyphenylamino)-4:6-dichloro-1z3z5-triazine, 2-(3- be used to obtain the amines of Formula I used in this carboxyphenylamino)-4:6-dichloro-1:3z5-triazine, 2-(4'- process of the invention there may be mentioned 2-methcarboxyphenylamino)-4:6-dichloro-1:3:5-triazine, 2 (4- oXy-5-methy1aniline, m-toluidine, 2:5-dimethoxyaniline, hydroxy-3' carboxyphenylamino) 4:6 dichloro-l :325- l-naphthylamine, 2-methoxy-1-naphthy1amine, aniline, triazine, 2-phenoxy-4z6-dichloro-1:325-triazine and 2- anthranilic acid, o-anisidine, 2-methoxy-l-naphthylamineamino-4:6-dibromo-l:3z5-triazine. 6-su1phonic acid, 1-naphthylamine-6-sulphonic acid, 1- According to a further feature of the invention there is naphthylamine-7-sulphonic acid, 4-acetylamino-2-arnin0- provided an alternative process for the manufacture of anisole, m-aminoacetanillde, 4-benzoylamino-2-amin0- the new azo dyestuffs, as hereinbefore defined, which anisole, 4-acetylamino-2-aminobenzoic acid, m-chlorocomprises treating an azo compound of the formula:

(En-111m! OH N -Q i N H A N-NGN N L J aniline, m-anisidine and 2-amino-4methoxyphenoxyacetic Formula V acid. 0

The coupling components of Formula II may themwherein A, B, R, m, n, and p have the meanings stated selves be obtained by treating a naphthol sulphonic acid above, with a triazine of Formula IV as hereinbefore of the formula: defined.

(IJn-r ZH r This alternative process of the invention may be con- OH N 00G 1 veniently carried out by adding an aqueous solution of N H the azo compound of Formula V to a solution or suspension of the triazine of Formula IV in Water or in a mix- 9- ture of acetone and water, heating the resulting mixture,

preferably at a temperature between 40 and C., adding sodium carbonate to maintain the pH of the mixture between 5 and 7.5, and filtering off the azo dyestuti which 2mm is precipitated. If desired, sodium chloride can be added Formula III to ensure complete precipitation of all the azo dyestuif.

The azo compounds of Formula V used in this alternative process of the invention may be obtained by coupling a diazotised amine of Formula I, as hereinbefore defined,

wherein R, m, n, and p have the meanings stated above, with a triazine of the formula:

% with a naphthol sulphonic acid of Formula III, as hereinbefore defined. N According to a further feature of the invention there is ig g provided a modified process for the manufacture of the new azo dyestuffs, as hereinbefore defined, wherein Y represents an amino group or an aryloxy, alkylamino radi- Formula IV cal or an arylamino, carboxyarylamino or sulphoary1- wherein X and Y have the meanings stated above. amino radical wherein the aryl residue contains not more than 12 carbon atoms, which comprises treating an azo dyestuff of the formula:

wherein A, B, R, X, m, n, and p have the meanings stated above, with a compound of the formula: HD wherein D represents an amino group or an aryloxy or alkylarnino radical or an arylamino, carboxyarylamino or sulphoarylamino radical wherein the aryl residue contains not more than 12 carbon atoms.

This modified process of the invention may be conveniently carried out by heating an aqueous solution of a dyestuff wherein Y represents a halogen atom with one wherein A, B, R, X, Y, m, n, and p have the meanings stated above and Z represents a metallisable group.

Cit-1 mm Z 0H N G] A-N=N- B N=N J (SOsH) Formula VII molecular proportion of a compound of the formula: HD, as hereinbefore defined, at a temperature between 40 and C., adding sodium carbonate to maintain the pH of the mixture between 7.0 and 7.2, adding sodium chloride and filtering off the dyestuff which is precipitated.

As examples of compounds of the formula: H-D which may be used in the modified process of the invention there may be mentioned phenol, ammonia, aniline, 2-sulphoaniline, 3-s'ulphoaniline, 4-sulphoaniline, 2-carboxyaniline, 3-carboxyaniline, 4-carboxyaniline, 3:5-disulphoaniline, N-methylaniline, 4-hydroxy-3-carboxyaniline, 2-naphthylamine-4:8-, 517-, 6:8- or 3:6-disulphonic acid, metanilic acid and 1-naphthylamine-4-sulphon'ic acid, or the alkali metal salts of these compounds.

The azo dyestuffs of Formula VI may themselves be obtained by treating an azo compound of Formula V with cyanuric chloride or cyanuric bromide.

A preferred class of the new azo dyestuffs, as hereinbefore defined, are those dyestuffs which contain a metallisable group in the phenylene or naphthylene radical represented by B, the said metallisable group being in an ortho position to the azo bond which links B with the naphthalene nucleus, as this preferred class of dyestuffs yield metal complexes which, when applied to cellulose textile materials, give dyeings which have excellent fastness to light.

According to a further feature of the invention there are provided as new metal-containing azo dyestuffs the metal complexes of the azo dyestuffs of the formula:

% X life O wherein A, B, Z, R, m, n and p have the meanings stated above, with a metallising agent and with a triazine of Formula IV, as hereinbefore defined.

The aminoazo compound may be treated with the triazine and then with the metallising agent, but it is preferred to treat the amino azo compound with the metallising agent and subsequently treat the metal complex so obtained with the triazine.

This process of the invention may be conveniently carried out by heating an aqueous solution of the aminoazo compound with an aqueous solution of the metallising agent, adding an aqueous solution of the metal complex so formed to a solution or suspension of the triazine in water or in an aqueous solution of acetone, maintaining the pH of the mixture between 6 and 7 by adding sodium carbonate and filtering off the dyestuif which is precipitated. If desired sodium chloride can be added to ensure complete precipitation of all the dyestuff.

As examples of metallising agents which may be used in the process of the invention here may be mentioned copper sulphate, cuprammonium sulphate, copper acetate, nickel acetate, cobalt sulphate and chromium formate, but the preferred metallising agents are agents which yield copper.

As examples of triazines of Formula IV which may be used in this process of the invention there may be mentioned 2-phenyl-4 6-d-ich1oro-1 :3 S-triazine, 2-phenoxy- 4:6-dichloro-1 :3 :5 -triazine, 2-amino-4 6-dichloro-1 :3 :5-

triazine, 2-di(/3-hydroxyethyl)amino-4:6-dichloro-l:315- amino-8-naphthol-4-sulphonic acid and l-amino-8-naphtriazine, 2-phenylamino-4:6-dichloro-lz3z5-triazine, 2-(2'- thol-3-sulphonic acid.

sulphophenylamino)-4:6-dichloro 1:3:5 -triazine, 2-(3'- According to a further feature of the invention there sulphophenylamino) 4:6 dichloro-l :3 :S-triazine, 2-(4- is provided a modified process for the manufacture of the sulphophenylamino) 4:6 dichloro 1:3:5 triazine, 2- 5 new metal-containing azo dyestuifs, as hereinbefore deamino-4z6-dibromo 123:5 triazine, 2-methylamino-4:6 fined, wherein Y represents an amino group or an aryloxy dichloro-l:3 :S-triazine and 2-dimethylamino-4:6-dichloor alkylamino radical or an arylamino, carboxyarylamino ro-lz3z5-triazine. or sulphoarylamino radical wherein the aryl residue con- The aminoazo compounds of Formula VII used in this tains not more than 12 carbon atoms, which comprises process of the invention may be obtained by diazotising treating a metal complex of an azo dyestuff of the fora primary amine of the formula: A--NH wherein A has mula:

the meaning stated above, coupling the diazo compound Formula VIII so formed with a para coupling amine of the formula: wherein A B, X Z, m n and I) have the meanings stated above, with a compound of the formula: DH as herein'before defined.

This modified process of the invention may be conveniently carried out by heating an aqueous solution of the metal complex of an azo dyestutf of Formula VIII with one molecular proportion of a compound of the wherein B and Z have the meanings formula: DH, as hereinbefore defined, at a temperaazotising and coupling under alkahne conditions with a mm between and adding Sodium carbonate naphthol sulphonic acid of Formula III, as hereinbefore 3D to maintain the PH f the mixture between 7 and 7 definedaddin sodium chloride and filtering off the dyestutf which As examples of primary amines of the formula: is precipitated z which may be used to Obtam the ammoazo The metal complex of an azo dyestuif of Formula VIII compounds used in this process of the invention there I may be obtained by treating an aminoazo compound of may be mentloned aniline, orthamhc acld, metamhc acid,

40 Formula VII with a metallising agent and then with sulphanilic acid, S-amino-Z-hydroxybenzoic acid, S-aminocyanuric chloride or cyanuric m m Y P acid, l'mflphthylamim f The new azo dyestulfs and new metal-containing azo P acld; 2-naphthylamme s'sulphomc dyestuffs, as hereinbefore defined, are valuable for colour- P Q P and, ing cellulose textile materials, for example cotton, viscose P acld, f rayon and linen textile materials. For colouring the cellu- Phomc acld, 3-chloro-4jmethylamhne-6-sulphonlc f g lose textile materials the new dyestuffs may be applied by chloroaniline-2-sulphon1c acid, 4-chloro-3-rnethylaml neeither a dyeing or a printing method preferably in com 6-sulphonic acid, 4 -chlor o aniline-3:sulphonic ac d, a junction with a treatment with an acid-binding agent, for ll4-dlsulphonlc 391d, anlllneaiidlslllphomc 301d F? example by the methods disclosed in British specification nilic acid, 5-sulphoanthranilic acid, 4-sulphoanthran1l1c 797,946 When so appued to Cellulose textile acid, Smitfoanthranilic acid, Y terials the new dyestuiis, as hereinbefore defined, yield 6'slllphonic acid, F'fithoxy-1'naphthylamme'fi'sulphPmc reddish-blue to greenish-blue shades possessing excelacid, 2-naphthylarn1r1e-1:5-, 3:6-, 4:8-, 517- 0r 6I8-d1w1- lent fastness to wet treatments such as washing and to phonic acid, l-amino-8-naphthol-3:6-disulphonic acid, 2- light naPhthylamine'l'sulphonic acid and 4'sulpho'z'amlno' A preferred class of the new dyestuffs of the invention amsole. are the copper complexes of the azo dyestuffs which, in As examples of the Para couplmg ammes whlcl} y the form of the free acids, are represented by the formula:

be used to obtain the aminoazo compounds used in this process of the invention there may be mentioned 2:5-dimethoxyaniline, 2-methoxy-5-methylaniline, anthranilic C H N acid, 2 methoxy- 1 naphthylamine-6-sulphonic acid, 2- ethoxy-l-naphthylamine-6-sulphonic acid, o-anisidine, 4- 3 I fi-X acetylamino-Z-aminoanisole, 4 acetylamino-Z-aminoben- N N zoic acid, 4-benzoylamino-Z-aminoanisole and 2-amino-4- A'-'N=N E N=N methoxyphenoxyacetic acid.

As examples of the naphthol sulphonic acids of For- 11035 Y mula III which may be used to obtain the aminoazo com- T pounds used in this process of the invention there may be mentioned 1 amino 8 naphthol-3:6 disulphonic acid,

1-(3- or 4-aminobenzoylamino)-8-naphthol 3:6 disulphonic acid, l-N-ethylamino-8-naphthol-3:6-disulphonic wherein B, X, Y and n have the meanings stated above, acid, 1-N-butylamino-8-naphthol 3:6 disulphonic acid, A represents a phenyl or naphthyl radical containing at 1-amino-8-naphthol-4:G-disulphonic acid, 1-(3- or 4- least one sulphonic acid group, Z represents a hydroxy aminobenzoylamino) 8- naphthol 4:6disulphonic acid, or methoxy group, and one T represents a sulphonic acid 1 -N- butylamino 8 naphthol-4:6-disulphonic acid, 1- group and the other T represents a hydrogen atom. In

9 this preferred class X preferably represents a chlorine atom, Y preferably represents a sulphoanilino or disulphoanilino radical and 11 preferably represents 1.

The invention is illustrated but not limited by the following examples in which the parts and percentages are by weight:

Example 1 Diazotised orthanilic acid is coupled with Z-methoxy-S- methylaniline and the aminoazo compound so obtained is diazotised and coupled under alkaline conditions with an equirnolecular proportion of l-amino 8-naphthol-3z6- disulphonic acid. The aminodisazo compound so obtained is converted to the copper complex by heating with an aqueous solution of cuprammonium sulphate for 20 hours at a temperature between 95 and 100 0., adding salt and filtering off the precipitated copper complex.

A solution of 15.1 parts of the above copper complex in 300 parts of water is added with stirring to a suspension of 3.8 parts of 2-amino-4z6-dichloro-l23:5-triazine in a mixture of 30 parts of acetone and 100 parts of water. The mixture is then stirred for 2 hours at a temperature of 50 C., the pH of the mixture being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. 80 parts of sodium chloride are added, the precipitated dyestufi is then filtered oil and dried at 30 C. On analysis the dyestufl so obtained is found to contain 1.0 atom of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields navy blue shades possessing excellent fastness to washing and to light.

Example 2 In place of the 3.8 parts of 2-amino4:6-dichlorol:3 :5- triazine used in Example 1 there are used 4.7 parts of 2- phenoxy-4: 6-dichloro-l 3 S-triazine.

On analysis the dyestuff so obtained is found to contain 0.98 atom of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields navy blue shades possessing excellent fastness to washing and to light.

Example 3 Diazotised orthanilic acid is coupled with Z-methoxyaniline and the aminoazo compound so obtained is diazotised and coupled under alkaline conditions with an equimolecular proportion of 1-amino-8-naphthol-3:6-disulphonic acid. The aminodisazo compound so obtained is converted to the copper complex by heating with an aqueous solution of cuprammonium sulphate for 20 hours at a temperature between 95 C, and 100 C., adding salt and filtering off the precipitated copper complex.

A solution of 30 parts of the above copper complex in 250 parts of water is added with stirring to a suspension of 7.6 parts of cyanuric chloride in a mixture of 80 parts of acetone, 150 parts of ice and 150 parts of water, the temperature being maintained between and C. by external cooling. The mixture is stirred for 1 hour and 23 parts of a aqueous solution of sodium carbonate are then added. To the solution so obtained is added a solution of 8.1 parts of sodium metanilate in 50 parts of water. 38 parts of a 10% aqueous solution of sodium carbonate are then added and the mixture is heated for 2 hours at a temperature between 40 and 45 C., the pH of the mixture being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. 55 parts of sodium chloride are added and the dyestuif, which is precipitated, is filtered off and dried. On analysis the dyestulf so obtained is found to contain 1.1 atoms of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction With a treatment with an acid-binding agent the dyest-ufi gives navy blue shades possessing excellent fastness to washing and to light.

Example 4 Diazotised Z-naph-thylamine 4:8-disulphonic acid is coupled with Z-methoxyaniline and the aminoazo compound so obtained is diazotised and coupled under talkaline conditions with an equimolecular proportion of 1- amino-S-naphthol 3:6-disulphonic acid. The aminodisazo compound so obtained is heated with an aqueous solution of cuprammonium sulphate for 20 hours at 'a temperature between and C., salt is then added and the copper complex which is precipitated is filtered off and dried.

A solution of 10 parts of the above copper complex is added stirring to a suspension of 3.6 parts of 2-(4'sulphoanilino)-4: 6-dichloro-1 :3 :S-triazine in a mixture of 50 parts of acetone and parts of water. The mixture is then stirred for 2 hours at a temperature of 4550 C., the pH of the mixture being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. 10 parts of sodium chloride are then added and the dyes-tuif which is precipitated is filtered off and dried. On analysis the dyestuif is found to contain 1.1 atoms of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestufl. yields blue shades possessing excellent fastness to washing and to light.

Example 5 In place of the 3.6 parts of 2-(4'-sulphoanilino)-4:6- dichloro-1:3:5-triazine used in Example 4 there are used 3.6 par-ts of 2-(3'-sulphoanilino)-4:6-dichloro-1:3:5-triazine.

On analysis the dyestulf so obtained is found to contain 0.83 atom of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid binding agent the dyestuff yields blue shades possessing excellent fastness to washing and to light.

The following table gives funther examples of the shades obtained on cellulose textile materials from the dyestuffs obtained by the method described in Example 3 above by diazo-tising the amine listed in the second column of the table, coupling with the para coupling amine listed in the third column of the table, rediazotising and coupling with the coupling component listed in the fourth column of the table, treating the resulting disazo compound with a coppering agent, condensing the resulting copper complex with cyanuric chloride and finally reacting with the amino compound listed in the fifth column of the table.

Shade ob- Ex. Amine Para coupling amine Coupling component Amino compound tained on cellulose textile materials 6 Orthanilic acid 2methoxyaniline l-aln lcesnaphthol 3i6-diS11lpll0l1lC Sodium sulphanilate Navy blue.

aci 7 Metanilic acid 2-met oxy-5-pqet ylfl fid Sodium metanilate-.- Blue. s 2-naphtl1ylamine 6:8disulphonic Z-rnethoXramlme. do Dark blue.

ac 9 Orthanilic acid 2-methoxy-5-methy1anilme.. l-afllt lo-s-naphthol-i:B-disulphonrc o,

an 10 Aniline 2zadisulphonic acid .do l-am iio-snaphthol3:6-disulphonlc Blue.

aci 1L. Z'naphthyIamine 3:6:Hrisulphondo do Do.

10 am 12.- Sulphanilic acid 2-rne hoxy do Sodium metanilate Navy blue.

Example 13 Diazotised 2-naphthylamine-4:S-disulphonic acid is coupled with 2:5-dimethoxyaniline and the aminoazo compound so obtained is diazotised and coupled under alkaline conditions with an equimolecular proportion of 1- amino-8-naphthol-3:6-disu1phonic acid. The aminodisazo compound so obtained is heated with an aqueous solution of cuprammonium sulphate for 20 hours at a temperature between 95 and 100 C., salt is then added and the copper complex which is precipitated is filtered OE and dried.

A solution of 37.3 parts of the above copper complex in 280 parts of water is added with stirring to a suspension of 14 parts of 2(2-sulphoanilino)-4:6-dichloro- 1:3 :-triazine in a mixture of 50 parts of acetone and 100 parts of water. The mixture is then stirred for 1 hour at a temperature of 45 C., the pH of the mixture being maintained at 7 by the addition of a aqueous sodium carbonate. 60 parts of sodium chloride are then added and the dyestufi, which is precipitated, is filtered oil and dried. On analysis the dyestufii is found to contain 0.8 atom of organically bound chlorine for each disazo molecule present.

When appiled to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields blue shades possessing excellent fastness to washing and to light.

Example 14 Diazotised orthanilic acid is coupled with Z-methoxy- S-methylaniline and the aminoazo compound so obtained is diazotised and coupled under alkaline conditions with an equimolecular proportion of 1-arnino-8-naphtho1-3:6- disulphonic acid.

A solution of 28.7 parts of the above aminodisazo compound in 250 parts of water is added with stirring to Y a suspension of 7.6 parts of cyanuric chloride in a mixture of 80 parts of acetone, 150 parts of water and 150 parts of ice, the temperature of the mixture being maintained between 0 and 5 C. by external cooling. The mixture is then stirred for 1 hour and 23 parts of a 10% aqueous solution of sodium carbonate are added. To the solution so obtained is added a solution of 8.1 parts of sodium metanilate in 50 parts of water. 23 parts of a 10% aqueous sodium carbonate solution are then added and the mixture is heated for 2 hours at a temperature between 40 and 45 C., the pH of the mixture being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. 55 parts of sodium chloride are then added and the dyestul'f which is precipitated, is filtered off and dried. On analysis the dyestufi so obtained is found to contain 1.15 atoms of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestufi yields navy blue shades possessing excellent fastness to washing and good fastness to light.

Example 15 In place of the 8.1 parts of sodium metanilate used in Example 14 there are used 6.4 parts of the sodium salt of p-aminobenzoic acid. On analysis the dyestuif so obtained is found to contain 1.15 atoms of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuff yields navy blue shades possessing excellent fastness to washing and good iastness to light.

Example 16 Example 17 A solution of 20.9 parts of the disodium salt of l-N- butylamino-8-naphthol-3:6-disulphonic acid in 200 parts of water is added with stirring to a suspension of 9.5 parts of cyanuric chloride in a mixture of parts of acetone, 100 parts of water and 100 parts of ice. The resulting mixture is stirred for 2 /2 hours at a temperature between 0 and 3 C. and the pH of the mixture is then raised to 7 by the addition of a 10% aqueous solution of sodium carbonate. 4.7 parts of aniline are added and the mixture is stirred for 2 hours at a temperature between 40 and 45 C., the pH being maintained at 7 by the addition of a 10% aqueous solution of sodium carbonate. The solution is then cooled to a temperature between 0 and 10 C., and an aqueous suspension of diazotised 4-amino-2- methyl-S-methoxy-l 1-azobenzene-2 5'-disulphonic acid (which is obtained by adding a solution of 22.2 parts of the disodium salt of the above aminoazo compound and 3.8 parts of sodium nitrite in 200 parts of water to a mixture of 24 parts of a concentrated aqueous solution of hydrochloric acid and 200 parts of ice), is then added during 5 minutes while the temperature of the mixture is maintained between 0 and 7 C. Sodium carbonate is then added, during ten minutes, until the pH of the mixture is 7.5 and the mixture is stirred for 3 hours at a temperature between 0 and 5 C. parts of sodium chloride are then added and the dyestuff which is precipitated is filtered off, washed with 15 parts of a 10% aqueous solution of sodium chloride and dried. On analysis the dyestufi so obtained is found to contain 1.1 atoms of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuflf yields violet shades possessing good fastness to washing and to light.

Example 18 In place of the 30 parts of the copper complex used in Example 3 there are used 35.7 parts of the chromium complex which is obtained by coupling diazotised 2-naphthylamine-5:7-disulphonic acid with anthranilic acid in acid medium, diazotising the aminomonoazo compound so obtained, coupling the resulting diazo compound with 1- 13 amino-8-naphthol-3:6-disulphonic acid in alkaline medium and heating the aminodisazo compound so obtained with an aqueous solution of chromium acetate. On analysis the dyestuif so obtained is found to contain 0.85 atom of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestuif yields violet shades possessing good fastness to washing and to light.

Example 19 In place of the 30 parts of the copper complex used in Example 3 there are used 37.0 parts of the nickel complex which is obtained by coupling diazotised Z-naphthylamine- 5 :7-disulphonic acid with anthranilic acid in acid medium, diazotising the aminomonoazo compound so obtained,

l4 stufi so obtained is found to contain 0.91 atom of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestufi yields grey shades possessing good fastness to washing and to light.

The following table gives further examples of the shades obtained on cellulose textile materials from the dyestuffs obtained by the method described in Example 3 above by diazotising the amine listed in the second column of the table, coupling with the para coupling amine listed in the third column of the table, rediazotising and coupling with the coupling component listed in the fourth column of the table, treating the resulting disazo compound with a coppering agent, condensing the resulting copper complex with cyanuric chloride and finally reacting with the amino compound listed in the fifth column of the table.

Shade obtained Ex. Amine Para coupling amine Coupling component Amino compound OIItCGItlIIIIOSG ex 1 e materials 21- Orthanilic acid o-Anisidine 1-amino 8-naphthol-4:6- Metanilic acid Navy-blue.

disulphonic acid. 22." 2-naphthyiamine- 6:8- disulphonic do 1-an.iiuo'8-naphtl 1ol-3:6- Aniline Do.

acid. disulphonie acid. 23.-. 2-nap1hthylamine- 4:8- disulphonic 2-methoxy-5-methy1aniline d -d0 Do.

aci 24.- 2-Implthylamine-3zfiz8-trisulphor1ic do do p-Aminobenzoic acid. Do.

ac1 25. Orthanilic acid do l-amino-8'naphthol-4zfi- Sulphanilic acid Do.

disulphonic acid. 26. do l-amino-G-sulpho-2-naphthoxyacetic i-amino-8-naphthol-3z6- Metamlic acid Greenishacid. disulphonic acid. blue.

coupling the resulting diazo compound with 1-amino-8- naphthol-3:6-disulphonic acid in alkaline medium and heating the aminodisazo compound with an aqueous solution of nickel sulphate. On analysis the dyestulf so obtained is found to contain 1.1 atoms of organically bound chlorine for each disazo molecule present.

When applied to cellulose textile materials in conjunction with a treatment with an acid-binding agent the dyestutf yields violet shades possessing good fastness to washing and to light.

The following table gives further examples of the shades obtained on cellulose textile materials from the dyestuffs obtained by the methods described in Examples 1 and 4 above by diazotising the amine listed in the second column of the table, coupling with the para coupling amine listed in the third column of the table, rediazotising and coupling with the coupling component listed in the fourth column of the table, treating the resulting disazo compound with a coppering agent, and condensing the resulting copper complex with the triazine listed in the fifth column of the table.

Shade obtained Ex. Amine Para coupling amine Coupling component Triazine ontceltllililose ex e materials 27 Orthanilic acid 2-methoxy-5 methyl 1-amino-8-naphtho1-3:fi disul- 2-(3-sulphoani1ino)-4:G-dichloro- Navy-blue.

aniline. phonic acid. 1:3:5-tr1azine. I 28,..- do o-Ani irline do 2-(3:5-d1sulphoa.n1lino)-4:6-di- Do.

chl0ro-1z3z5-triazine. 29. 2-naphthylamine-4z8-disul- 2-methoxy-5-methyl y- 1 i 1 r -1= D phonic acid. aniline. tnazine. 30- 3-chloro-4-methyiani1ine-6- do do 2-(3 5-disulph0an lmo)-4:6-di- Do.

sulphonic acid. chloro-lz3z5-triazine. 31.- 4-aminoanisoie-3-su1phonic do l-amino-S-na hthol-4:6-disul- 2-(3-su1pl1oamlmo)-4:G-dichloro- Do.

acid. phonic aci 1:3:5-tr1az1ne. 32--- Aniline-2:5-disulphonic acid. do 1-(3-aminobenzoylamin0)-8- d0 Greenishnaphthol-azfi-disulphonic acid. blue.

Example In place of the parts of the copper complex used in Example 3 there are used 35.8 parts of the cobalt complex which is obtained by coupling diazotised 2-naphthylamine- 5 :7-disulphonic acid with anthranilic acid in acid medium, diazotising the aminomonoazo compound so obtained, coupling the resulting diazo compound with l-amino-8- naphthol-3 :6-disulphonic acid in alkaline medium, and heating the aminodisazo compound so obtained with an aqueous solution of cobalt acetate.

The following table gives further examples of the shades obtained on cellulose textile materials from the dyestuffs obtained by the method described in Example 14 by diazotising the amine listed in the second column of the table, coupling with the para coupling amine listed in the third column of the table, rediazotising and coupling with the coupling component listed in the fourth column of the table, condensing the resulting aminodisazo compound with cyanuric chloride and finally reacting with the amino compound listed in the fifth column of the On analysis, the dyetable.

Shade obtained Ex. Amine Para coupling amine Coupling component Amino compound ontceltlillilose ex e material 33--- Orthanilic acid 2-methoxy-1-naphthylamine- 1-amino-8-naphthol-3:6-disu1- fi-sulphonic acid. phonic acid. 34. 2-nophthylamine-4 B-disui- 2 5dimcthoxyaniline do phonic acid. 35 do do Snlphanilic Do. 36. 2-nailphtihylag1ine-3zfiz8'trlsul- 2-methoxy-5-methylanillne. p'Aminobenzolc acid Do.

p on c ac 37--- Metamllc acid rin 1-ar nino'8-na(phtho1-4:6 disu1- Aniline-3:5disu1phonic acid- Do.

p oruc aci 38- do do 1-amino-8-naphthol-3:B-disul- Metunillc acid Do.

phonic acid. 39- 2-aminophenol-4z6-dlsul- 2:5-dimethoxyaniline do ..do Greenlshphonic acid. blue.

What we claim is:

of azo dyestuffs of the formula:

sisting of sulfonated phenyl and naphthyl radicals on which any substituents are selected from the class consisting of chlorine, methyl, methoxy and hyn-1 2u-1/ droxy; 00113 on N 0/ \Q X 20 R is selected from the class consisting of hydrogen,

1 ll methyl and methoxy; N=N X represents a member selected from the class consisting of chlorine and bromme atoms; R Y Y represents a member selected from the class con- 25 sisting of amino and methoxy, phenoxy and phenylamino on which any substituents are selected from (80311)" the class consisting of sulfonic acid and carboxylic and the 1:1 copper-, 1:1-nickel-, 1:2-chromium and 1:2- acid radicals; and, cobalt complexes thereof, wherein n represents one of the numbers 1, 2, 3, 4 and 5.

A represents a member selected from the class con- 2.

01 NJ; SOaH 0--0u-( IIIHO\ /N I Q NH- H038 -s0;,H

SOZH

1 N-C S0311 (')-Cu-(|) IrH-O /N NH- SOzH SIOaH 0-Cu--(|J IfH-C /N N=O M M I I NE HOaS H3 H033 SOaH SlOsH O--Cu-(|) IIIHC\ /N N==O C -N=N- N=N I References Cited in the file of this patent UNITED STATES PATENTS 2,396,659 Kaiser Mar. 19, 1946 2,860,128 Gunst Nov. 11, 1958 2,945,021 Fasciati et a1 July 12, 1960 

1. A COMPOUND SELECTED FROM THE CLASS CONSISTING OF AZO DYESTUFFS OF THE FORMULA: 